A bis-calix[4]arene-supported [CuII16] cage
Abstract
Reaction of 2,2'-bis-p-tBu-calix[4]arene (H8L) with Cu(NO3)2·3H2O and N-methyldiethanolamine (Me-deaH2) in a basic dmf/MeOH mixture affords [CuII16(L)2(Me-dea)4(μ4-NO3)2(μ-OH)4(dmf)3.5(MeOH)0.5(H2O)2](H6L)·16dmf·4H2O (4), following slow evaporation of the mother liquor. The central core of the metallic skeleton describes a tetracapped square prism, [Cu12], in which the four capping metal ions are the CuII ions housed in the calix[4]arene polyphenolic pockets. The [CuII8] square prism is held together “internally” by a combination of hydroxide and nitrate anions, with the N-methyldiethanolamine co-ligands forming dimeric [CuII2] units which edge-cap above and below the upper and lower square faces of the prism. Charge balance is maintained through the presence of one doubly deprotonated H6L2- ligand per [Cu16] cluster. Magnetic susceptibility measurements reveal the predominance of strong antiferromagnetic exchange interactions and an S = 1 ground state, while EPR is consistent with a large zero-field splitting.
- Authors:
-
[1];
[1];
[1];
[2];
[3];
[4];
[5];
[1]
- University of Edinburgh, Scotland (United Kingdom)
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- University of Manchester (United Kingdom)
- University of Copenhagen (Denmark)
- Heriot-Watt University, Edinburgh, Scotland (United Kingdom)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); Engineering and Physical Sciences Research Council (EPSRC)
- OSTI Identifier:
- 2234075
- Grant/Contract Number:
- AC02-05CH11231; EP/N01331X/1; EP/W014521/1; EP/V035231/1
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 52; Journal Issue: 26; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Wilson, Lucinda R. B., Coletta, Marco, Singh, Mukesh K., Teat, Simon J., Brookfield, Adam, Shanmugam, Muralidharan, McInnes, Eric J. L., Piligkos, Stergios, Dalgarno, Scott J., and Brechin, Euan K. A bis-calix[4]arene-supported [CuII16] cage. United States: N. p., 2023.
Web. doi:10.1039/d3dt01448g.
Wilson, Lucinda R. B., Coletta, Marco, Singh, Mukesh K., Teat, Simon J., Brookfield, Adam, Shanmugam, Muralidharan, McInnes, Eric J. L., Piligkos, Stergios, Dalgarno, Scott J., & Brechin, Euan K. A bis-calix[4]arene-supported [CuII16] cage. United States. https://doi.org/10.1039/d3dt01448g
Wilson, Lucinda R. B., Coletta, Marco, Singh, Mukesh K., Teat, Simon J., Brookfield, Adam, Shanmugam, Muralidharan, McInnes, Eric J. L., Piligkos, Stergios, Dalgarno, Scott J., and Brechin, Euan K. Fri .
"A bis-calix[4]arene-supported [CuII16] cage". United States. https://doi.org/10.1039/d3dt01448g. https://www.osti.gov/servlets/purl/2234075.
@article{osti_2234075,
title = {A bis-calix[4]arene-supported [CuII16] cage},
author = {Wilson, Lucinda R. B. and Coletta, Marco and Singh, Mukesh K. and Teat, Simon J. and Brookfield, Adam and Shanmugam, Muralidharan and McInnes, Eric J. L. and Piligkos, Stergios and Dalgarno, Scott J. and Brechin, Euan K.},
abstractNote = {Reaction of 2,2'-bis-p-tBu-calix[4]arene (H8L) with Cu(NO3)2·3H2O and N-methyldiethanolamine (Me-deaH2) in a basic dmf/MeOH mixture affords [CuII16(L)2(Me-dea)4(μ4-NO3)2(μ-OH)4(dmf)3.5(MeOH)0.5(H2O)2](H6L)·16dmf·4H2O (4), following slow evaporation of the mother liquor. The central core of the metallic skeleton describes a tetracapped square prism, [Cu12], in which the four capping metal ions are the CuII ions housed in the calix[4]arene polyphenolic pockets. The [CuII8] square prism is held together “internally” by a combination of hydroxide and nitrate anions, with the N-methyldiethanolamine co-ligands forming dimeric [CuII2] units which edge-cap above and below the upper and lower square faces of the prism. Charge balance is maintained through the presence of one doubly deprotonated H6L2- ligand per [Cu16] cluster. Magnetic susceptibility measurements reveal the predominance of strong antiferromagnetic exchange interactions and an S = 1 ground state, while EPR is consistent with a large zero-field splitting.},
doi = {10.1039/d3dt01448g},
journal = {Dalton Transactions},
number = 26,
volume = 52,
place = {United States},
year = {Fri Jun 09 00:00:00 EDT 2023},
month = {Fri Jun 09 00:00:00 EDT 2023}
}
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